Methyl butyrate, oxidation

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

Fig. 11. The effect of temperature on the maximum rate of oxidation (in torr. min ) of esters [93]. (1) Methyl acetate. (2) Methyl formate. (3) Methyl propionate. (4) Ethyl formate. (5) Methyl butyrate. (6) Propyl formate.

METHYL BUTYRATE or METHYL A-BUTYRATE (623-42-7) Forms explosive mix ture with air (flash point 57°F/I4°C cc). Incompatible with strong acids, nitrates, oxidizers. 

Figure 3.13 Headspace analysis of volatiles of whole milk powder stored in air at 40 C (peroxide value 1.01). 1 = pentanone 2 = pentanal 3 = methyl butyrate (internal standard) 4 = hexanal 5 = heptanone 6 = heptanal 7 = octanal 8 = octanoic 9 = nonanal. Chromatographic conditions were as in Fig. 3.12. Reproduced from Ulberth, F. and Roubicek, D., Monitoring of oxidative deterioration of milk powder by headspace gas chromatography. International Dairy Journal, 5, 523-31, 1995.

In addition, it has been shown that nucleophilic substitution reactions of mPEG-alk-oxides with ethyl 5-bromovalerate and ethyl 4-bromo-4-methyl butyrate, yield mPEG-ethyl valerate and mPEG-ethyl 2-methyl butyrate respectively, which upon hydrolysis should afford the corresponding free acids [81,82]. Presumably these reactions also give elimination products, as indicated for ethyl 3-bromopropionate. 

Baek et al. [110] prepared pyrrolidium-based ILs carrying different substituents including butyl, butyronittile, pentenyl, and methyl butyrate (Scheme 8.7). The nitrile- and ester-functionalized ILs show higher viscosities and lower conductivities than the other two. Their potential windows (vs. Li/LP) fall in the range of 4.19. 97 V and are primarily dependent on the oxidation power of the functional group on cations. It was also found that the peak currents at the reduction on the graphite electrode were 100 times stronger in butyl- and pentenyl-substituted ILs than in nitrile- and butyrate-functionalized ILs. 

The OH-initiated oxidation of methyl n-butyl ether has been studied in detail by Aschmann and Atkinson (1999a). Observed products, with molar yields in parentheses, were as follows methyl formate (51 11%), propanal (43 6%), butanal (4.5 1%), methyl butyrate ( 1.6%), and CH3C(0)CH2CH20CH3 and/or CH3CH2C(0)CH20CH3 (19 4%). Products with molecular weights of 118, 149, and 165, corresponding to five-carbon hydroxycarbonyls, nitrates, and hydroxynitrates, were also identified. 

Production of maleic anhydride by oxidation of / -butane represents one of butane s largest markets. Butane and LPG are also used as feedstocks for ethylene production by thermal cracking. A relatively new use for butane of growing importance is isomerization to isobutane, followed by dehydrogenation to isobutylene for use in MTBE synthesis. Smaller chemical uses include production of acetic acid and by-products. Methyl ethyl ketone (MEK) is the principal by-product, though small amounts of formic, propionic, and butyric acid are also produced. / -Butane is also used as a solvent in Hquid—Hquid extraction of heavy oils in a deasphalting process. 

Poly(ethylene terephtlhalate) Phenol-formaldehyde Polyimide Polyisobutylene Poly(methyl methacrylate), acrylic Poly-4-methylpentene-1 Polyoxymethylene polyformaldehyde, acetal Polypropylene Polyphenylene ether Polyphenylene oxide Poly(phenylene sulphide) Poly(phenylene sulphone) Polystyrene Polysulfone Polytetrafluoroethylene Polyurethane Poly(vinyl acetate) Poly(vinyl alcohol) Poly(vinyl butyral) Poly(vinyl chloride) Poly(vinylidene chloride) Poly(vinylidene fluoride) Poly(vinyl formal) Polyvinylcarbazole Styrene Acrylonitrile Styrene butadiene rubber Styrene-butadiene-styrene Urea-formaldehyde Unsaturated polyester... 

Acetanilide and maleic acid are condensed to give /3-(p-acetaminoben2oyl)acrvlic acid which is hydrogenated to give methyl- y-(p-aminophenyl)butyrate. That is reacted with ethylene oxide and then with phosphorus oxychloride to give the methyl ester which is finally hy-droly2ed to give chlorambucil. 

Deuteration studies with acetic acid-d4 (99.5% atom D) as the carboxylic acid building block, ruthenium(IV) oxide plus methyl iodide-d3 as catalyst couple and 1/1 (C0/H2) syngas, were less definitive (see Table III). Typical samples of propionic and butyric acid products, isolated by distillation in vacuo and glc trapping, and analyzed by NMR, indicated considerable scrambling had occurred within the time frame of the acid homologation reaction. 

In a Michael-type addition 192 is converted by treatment with mesityl oxide (207) or methyl acrylate (209) under equal conditions (TiCl4) to 1 -phenyl-3,3-di-methyl-l,5-hexanedione (208) and methyl 7-benzoyl-butyrate (210)14i respectively. 193 reacts with meta-chloroperbenzoic acid (87) to yield 2-trimethylsiloxy-cyclohexanone (2ii)142 ... 

Mixed ethers result when alcohols and phenols are used with thoria at 390°—420° and esterification takes place when alcohol and acid interact at 350°-400°. Esterification10 is more complete in the presence of titanic oxide at 280°—300°. One molecule of acid is used with twelve molecules of alcohol, and in this way methyl, ethyl, propyl, butyl, and benzyl esters have been prepared from acetic, propionic and butyric acids. 

Secondary and tertiary alkyl bromides react with active zinc at ambient temperature. However, the reaction time for the oxidative addition can be shortened by heating the reaction mixture at reflux in THF. Methyl 3-bromo-butyrate gives the organozinc bromide intermediate upon reaction with active zinc and reacts with 2-cyclohexen-l-one to afford the 1,4-addition product (Protocol 6, Scheme 2.3).14... 

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